CN111187927A - Method for selectively sulfating and recovering rare earth in neodymium iron boron waste - Google Patents
Method for selectively sulfating and recovering rare earth in neodymium iron boron waste Download PDFInfo
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- CN111187927A CN111187927A CN202010100059.3A CN202010100059A CN111187927A CN 111187927 A CN111187927 A CN 111187927A CN 202010100059 A CN202010100059 A CN 202010100059A CN 111187927 A CN111187927 A CN 111187927A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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Abstract
The invention discloses a method for selectively sulfating and recovering rare earth in neodymium iron boron waste, which comprises the following steps: the neodymium iron boron waste is crushed, ground, oxidized and roasted to be completely oxidized, the oxidized material is ground to 3-100 mu m and mixed with solid ferric sulfate to be pressed into blocks or SO is directly used3‑SO2‑O2The mixed gas is subjected to selective sulfating roasting at the temperature of 600-750 ℃, the rare earth elements are converted into sulfate, and the iron elements are still Fe2O3The other elements are substantially in the oxide state. After the selective sulfating roasting is finished, the material is soaked in water, filtered and separated, and Fe is used as Fe2O3The rare earth enters the filter residue in a form, and the rare earth enters the leaching solution in a sulfate form. The recovery rate of rare earth in the leaching solution reaches more than 95 percent, and the leaching solution does not need further purification and deironing treatment, so thatDirectly enters an extraction separation line of a rare earth separation plant. The method has the advantages of simple process flow, good controllability, low consumption of sulfation reactant and easy recovery of reaction tail gas, and realizes clean and efficient recovery of rare earth in the neodymium iron boron waste.
Description
Technical Field
The invention relates to the technical field of resource recovery, in particular to a method for selectively sulfating and recovering rare earth in neodymium iron boron waste.
Background
Because of its excellent comprehensive magnetic properties, neodymium iron boron has been widely used in many fields such as electronic information, wind power generation, new energy automobile, intelligent manufacturing, etc., and will have a wider market demand space in the future. The Nd-Fe-B contains about 28-35% of rare earth elements RE (Nd, Pr, Dy, Tb, etc.), and the balance of the composition is 60-70% of Fe, 1.0-1.2% of B and 3-5% of a small amount of additive elements (Al, Cu, Co, Nb, Zn, Ga, etc.). In the links of alloy smelting, powder making, sintering, cutting, grinding and the like of the neodymium iron boron production process, certain waste materials are generated, and the total content of the waste materials is about 30%. With the rapid increase of the demand of neodymium iron boron, the precious elements such as Nd, Pr, Dy, Tb, etc. in the rare earth resources are greatly consumed, which causes the problem of unbalanced utilization of the rare earth resources. The recovery of relevant rare earth elements from the waste materials generated in the preparation and processing process of the neodymium iron boron material and the waste materials which are used for a long time and have failure is an important measure for solving the problem and is also an important problem facing the sustainable development of the rare earth permanent magnet material industry.
The methods for recovering rare earth from neodymium iron boron waste at home and abroad are various, and can be mainly divided into hydrometallurgy, pyrometallurgy, chloridizing metallurgy and the like. The wet recovery method has the advantages that the high-purity rare earth solution can be obtained through the processes of impurity removal, purification and the like, and the method can be matched with a subsequent rare earth separation factory and the like, and has a leading position in the field of recovery of rare earth secondary resources. The wet recovery method of neodymium iron boron waste mainly comprises a hydrochloric acid total dissolution method, a sulfate double salt precipitation method, a hydrochloric acid optimum dissolution method, a sulfation-selective roasting-water leaching method and the like. The rare earth leaching process by the hydrochloric acid total dissolution method and the sulfuric acid complex salt precipitation method has obvious defects. All elements in the neodymium iron boron waste are converted into corresponding chlorides or sulfates by using hydrochloric acid or sulfuric acid and the like, so that the using amount of acid and alkali in the process is large, a large amount of iron-containing waste liquid needs to be subjected to impurity removal and purification treatment, and the consumption of reagents is large;in addition, the process flow is long and the operating environment is severe. The hydrochloric acid optimum dissolution method adopts oxidizing roasting-hydrochloric acid to dissolve and leach rare earth, and utilizes Fe in roasting material2O3The rare earth is difficult to dissolve in hydrochloric acid, the rare earth is preferentially leached, the consumption of acid is reduced, and the process flow is relatively short, but the method has the defects that a small amount of iron still enters the leaching solution in the process of leaching the rare earth by using the hydrochloric acid, the leaching solution still needs to be purified and deironing, and a certain amount of rare earth is lost in the process of adjusting the pH value of the solution and precipitating and deironing. A process for reclaiming rare-earth elements from Nd-Fe-B by sulfating, selective calcining and water immersion includes such steps as oxidizing and calcining the Fe-B powder, converting it to sulfate mixture at low temp by sulfuric acid, heating to 700 deg.C, selective calcining for selectively decomposing the sulfate of non-rare-earth elements, immersing in water, and removing Fe2O3Form separation, the recovery rate of the rare earth reaches 95-100%, and the purity of the rare earth reaches more than 98%. However, the process still adopts complete sulfation, which has the disadvantages of high acid consumption, long time of sulfation step, low production efficiency and relatively long flow.
Disclosure of Invention
In order to overcome and solve the defects of the process for recovering rare earth by hydrometallurgy in the prior art, the invention provides a method for selectively sulfating and recovering rare earth in neodymium iron boron waste, which has the advantages of high rare earth recovery rate, high rare earth solution purity, simple operation, short process flow and less reagent consumption.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for selectively sulfating and recovering rare earth in neodymium iron boron waste comprises the following steps:
s1, preprocessing neodymium iron boron waste materials: crushing, grinding and oxidizing and roasting the unoxidized neodymium iron boron waste or partially oxidized neodymium iron boron waste, and completely oxidizing elements in the neodymium iron boron waste into corresponding high-valence oxides;
s2, sulfating the fully oxidized neodymium iron boron material, converting the rare earth elements in the neodymium iron boron waste material into corresponding rare earth sulfate, wherein the iron element is still Fe2O3State, other element ownerIs in an oxide state, and a small part is in a sulfate state;
and S3, putting the sulfated and roasted material into water, filtering and washing to obtain the pure rare earth sulfate leaching solution.
In some embodiments of the invention, the rare earth in the neodymium iron boron waste is mainly Nd after being oxidized and roasted2O3And NdFeO3Two structural types of phase forms exist to improve the rare earth recovery of the subsequent selective sulfation-water leaching process.
In some embodiments of the present invention, the fully oxidized ndfeb material is further ground to a particle size of 3 to 100 μm before sulfation treatment. The material after the oxidizing roasting is finely ground, on one hand, the particle size of the roasted material is easily increased because the material is sintered in the oxidizing roasting process; on the other hand, the fine material granularity can provide excellent dynamic conditions for the selective sulfating roasting process, and improve the recovery rate and the recovery efficiency of the rare earth.
In some embodiments of the invention, the sulfation treatment in S2 comprises the steps of: uniformly mixing the finely ground neodymium iron boron oxide material and a solid sulfation reactant, briquetting, and then selectively roasting, or directly placing the finely ground neodymium iron boron oxide material in a gas sulfation reactant for selective sulfation roasting.
In some embodiments of the invention, the solid sulfation reactant is anhydrous ferric sulfate or ferric sulfate with crystal water.
In some embodiments of the invention, the gaseous sulfation reactant is flue gas SO of oxidative roasting and/or sulfation roasting of sulphide ores3-SO2-O2And (4) mixing the gases.
In some embodiments of the invention, the solid sulfating reagent is added in an amount to oxidize RE in the neodymium iron boron material2O31.0-3.0 times of theoretical amount when the sulfate is completely sulfated; the RE2O3Comprising a single RE2O3And NdFeO3RE in (1)2O3。
In some embodiments of the invention, the conditions of the selective roasting or selective sulfatizing roasting are: roasting at 600-750 ℃ for 0.5-3 h.
In some embodiments of the invention, in S3: adding the material after sulfating roasting treatment into deionized water at 25-50 ℃, stirring for 1-3 hours, filtering, and washing to obtain pure rare earth sulfate leaching solution and Fe2O3The main filtrate.
The chemical reaction involved in the selective sulfating roasting process of the oxidized and roasted material at the temperature of 600-750 ℃ is as follows:
1)Fe2(SO4)3overall reaction equation for sulfating different kinds of rare earth oxide-containing phases:
RE2O3+Fe2(SO4)3＝RE2(SO4)3+Fe2O3reaction scheme 1
REFeO3+Fe2(SO4)3＝RE2(SO4)3+3/2Fe2O3Reaction formula 2
REBO3+Fe2(SO4)3＝RE2(SO4)3+3/2B2O3Reaction formula 3
2)Fe2(SO4)3The decomposition process of (2):
Fe2(SO4)3＝Fe2O3+3SO3reaction formula 4
Or Fe2(SO4)3＝Fe2O3+3SO2+3/2O2Reaction formula 5
3) Released SO3Reaction with different types of rare earth-containing oxide phases:
RE2O3+3SO3＝RE2(SO4)3reaction formula 6
REFeO3+3SO3＝RE2(SO4)3+1/2 Fe2O3Reaction formula 7
REBO3+3SO3＝RE2(SO4)3+1/2 B2O3Reaction formula 8
The sulfation process of equations 2 and 3 can also be factually ascribed to RE2O3The sulfation process of (1). So that different kinds of rare earth-containing oxide phases can be converted into RE according to the mass conservation of RE elements2O3Amount, then according to total RE2O3The theoretical consumption of ferric sulfate can be calculated from the reaction equation 1.
The complete conversion of the rare earth oxide-containing substance to the rare earth sulfate can be ensured by adding ferric sulfate with different excess coefficients. Even the remaining part of the iron sulfate is decomposed into Fe according to the reaction formula 4 or 52O3And the filtered material is fed into the filter during filtration and separation. Thus avoiding Fe3+And the rare earth sulfate leachate is subjected to purification and deironing treatment, so that pure rare earth sulfate leachate is directly obtained and can be directly connected with the subsequent rare earth separation and extraction process.
To SO3-SO2-O2In the sulfation process of the mixed gas, different rare earth oxide-containing phases in the finely ground oxidizing roasting material directly react through the reaction formulas 6 to 8 to convert the rare earth oxide-containing phases into rare earth sulfate, and even if Fe exists in the material at the temperature of 600-750 DEG C2O3With SO3Reaction to form Fe2(SO4)3And also immediately decomposed by the reaction formula 4 or 5, so that the roasted material is immersed in water to obtain Fe3+And also does not enter the rare earth sulfate leaching solution.
The invention has the beneficial effects that:
(1) the invention utilizes the sulfation reactant to completely sulfate the neodymium iron boron waste in the oxidation material into the rare earth sulfate, while the iron element is still Fe2O3In the materials, other elements are mainly in an oxide state, and a small part of the elements are in a sulfate state;
(2) the method for recovering the rare earth elements in the neodymium iron boron waste has the advantages of simple and convenient process flow, high rare earth recovery rate, simplified subsequent treatment, less reagent consumption and the like;
(3) the process disclosed by the invention has applicability to the unoxidized and partially oxidized wastes of the neodymium iron boron, can be recycled in a large scale, and has considerable economic and social benefits.
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In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
Fig. 1 is a flow chart of a process for recovering rare earth from neodymium iron boron waste by selective sulfation according to an embodiment of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
As shown in fig. 1, the present invention provides a method for recovering rare earth from neodymium iron boron waste by selective sulfation, which comprises the following steps:
s1, preprocessing neodymium iron boron waste materials: crushing and grinding the unoxidized neodymium iron boron waste or partially oxidized neodymium iron boron waste, oxidizing and roasting for 2-8 hours at 500-900 ℃ in a natural air atmosphere or an oxygen-enriched atmosphere, completely oxidizing elements in the neodymium iron boron waste into corresponding high-valence oxides, and cooling to room temperature;
s2, finely grinding the material after oxidizing roasting, and controlling the particle size of the material to be 3-100 mu m; by adding solid sulfating reactant ferric sulfate or SO3-SO2-O2Roasting the mixed gas at the temperature of 600-750 ℃ to carry out sulfation treatment on the fully oxidized neodymium iron boron material, and converting rare earth elements in the neodymium iron boron waste into corresponding rare earth sulfate; when solid sulfating reactant ferric sulfate is added, the mixture is briquetted under the pressure of 10-30 Mpa, and the addition amount of the solid sulfating reactant ferric sulfate is that RE in the neodymium iron boron oxide material2O3The amount of the catalyst is 1.0 to 3.0 times of the theoretical amount when the catalyst is completely sulfated.
S3, putting the sulfated and roasted material into water, stirring for 1 hour at 25-50 ℃, filtering and washing to obtain pure rare earth sulfate leaching solution and Fe2O3The main filtrate.
Specifically, when a gaseous sulfation reactant is used, the generated gas or the un-participated SO is selectively roasted3-SO2-O2The mixed gas can be used for industrial acid preparation after being absorbed.
The following is further described in conjunction with the specific embodiments:
example 1
Taking 39.51g of neodymium iron boron oxide (containing 10g of rare earth oxide) with the particle size of less than 6 mu m, and adding 18.26g of Fe2(SO4)3·5H2O (added according to 1.3 times of theoretical amount), mixing the two materials uniformly, and pressing under 30Mpa
2 pieces of material. And putting the pressed material into a quartz material boat, and roasting in a constant-temperature area of a tubular atmosphere furnace. Heating the temperature in the tube furnace from room temperature to 700 ℃ at the speed of 10 ℃/min, and preserving the heat for 1.5 hours; the initial atmosphere is air and the tail gas is recovered with NaOH solution. And after the heat preservation is finished, cooling the roasted material to room temperature along with the furnace, and taking out. Grinding the cooled roasted material, adding 300ml of deionized water with the temperature of 25 ℃, and stirring for 1 hourThen, filtering and separating to obtain Fe2O3Mainly filter material and pure rare earth sulfate leaching liquid. The pH value of the obtained rare earth sulfate leaching solution is measured to be 6, and the concentration of iron ions is measured to be 0.023 g/L. The total content of the rare earth oxide precipitated in the rare earth sulfate leaching solution is measured by an oxalic acid gravimetric method, and the total recovery rate of the rare earth is 96.4 percent according to the ratio of the total content of the rare earth oxide in the initially added neodymium iron boron oxide material.
Example 2
39.51g of neodymium iron boron oxide (containing 10g of rare earth oxide) with the particle size less than 12 mu m is taken, 21.07g of Fe is added2(SO4)3·5H2O (added according to 1.5 times of theoretical amount), mixing the two materials uniformly, and pressing under 20Mpa
2 pieces of material. And putting the pressed material into a quartz material boat, and roasting in a constant-temperature area of a tubular atmosphere furnace. Heating the temperature in the tube furnace from room temperature to 750 ℃ at the speed of 10 ℃/min, and preserving the temperature for 1 hour; the initial atmosphere is air and the tail gas is recovered with NaOH solution. And after the heat preservation is finished, cooling the roasted material to room temperature along with the furnace, and taking out. Grinding the cooled roasted material, adding 300ml of deionized water with the temperature of 35 ℃, stirring for 1 hour, filtering and separating to obtain Fe2O3Mainly filter material and pure rare earth sulfate leaching liquid. The pH value of the obtained rare earth sulfate leaching solution is measured to be 6.5, and the concentration of iron ions is measured to be 0.021 g/L. The total content of the rare earth oxide precipitated in the rare earth sulfate leaching solution is measured by an oxalic acid gravimetric method, and the total recovery rate of the rare earth is 95.8 percent according to the ratio of the total content of the rare earth oxide in the initially added neodymium iron boron oxide material.
Example 3
Taking 39.51g of neodymium iron boron oxide (containing 10g of rare earth oxide) with the particle size of less than 30 mu m, and adding 25.28g of Fe2(SO4)3·5H2O (added according to 1.8 times of theoretical amount), mixing the two materials uniformly, and pressing under 30Mpa
2 pieces of material. And putting the pressed material into a quartz material boat, and roasting in a constant-temperature area of a tubular atmosphere furnace. Heating the temperature in the tube furnace from room temperature to 650 ℃ at the speed of 10 ℃/min, and preserving the temperature for 2 hours; the initial atmosphere is air and the tail gas is recovered with NaOH solution. And after the heat preservation is finished, cooling the roasted material to room temperature along with the furnace, and taking out. Grinding the cooled roasted material, adding 300ml of deionized water with the temperature of 25 ℃, stirring for 1 hour, filtering and separating to obtain Fe2O3Mainly filter material and pure rare earth sulfate leaching liquid. The pH value of the obtained rare earth sulfate leaching solution is measured to be 4.5, and the concentration of iron ions is measured to be 0.029 g/L. The total content of the rare earth oxide precipitated in the rare earth sulfate leaching solution is measured by an oxalic acid gravimetric method, and the total recovery rate of the rare earth is 95.1 percent according to the ratio of the total content of the rare earth oxide in the initially added neodymium iron boron oxide material.
Example 4
39.51g of neodymium iron boron oxide (containing 10g of rare earth oxide) with the granularity less than 6 mu m is flatly paved in a quartz boat, and the quartz boat is placed in a constant temperature area of a tubular atmosphere furnace for sulfating roasting. Heating the temperature in the tube furnace from room temperature to 700 ℃ at the speed of 10 ℃/min, and preserving the temperature for 2 hours; introducing SO into the furnace3-SO2-O2The mixed gas and tail gas are recovered by NaOH solution. And after the heat preservation is finished, cooling the roasted material to room temperature along with the furnace, and taking out. Grinding the cooled roasted material, adding 300ml of deionized water with the temperature of 30 ℃, stirring for 2 hours, filtering and separating to obtain Fe2O3Mainly filter material and pure rare earth sulfate leaching liquid. The pH value of the obtained rare earth sulfate leaching solution is measured to be 5, and the concentration of iron ions is measured to be 0.027 g/L. The total content of the rare earth oxide precipitated in the rare earth sulfate leaching solution is measured by an oxalic acid gravimetric method, and the total recovery rate of the rare earth is 95.3 percent according to the ratio of the total content of the rare earth oxide in the initially added neodymium iron boron oxide material.
Example 5
39.51g of neodymium iron boron oxide (containing 10g of rare earth oxide) with the granularity less than 12 mu m is flatly paved in a quartz boat, and the quartz boat is placed in a constant temperature area of a tubular atmosphere furnace for sulfating roasting. Tube furnaceHeating the mixture from room temperature to 750 ℃ at a speed of 10 ℃/min, and preserving heat for 3 hours; introducing SO into the furnace3-SO2-O2The mixed gas and tail gas are recovered by NaOH solution. And after the heat preservation is finished, cooling the roasted material to room temperature along with the furnace, and taking out. Grinding the cooled roasted material, adding 300ml of deionized water with the temperature of 25 ℃, stirring for 1.5 hours, filtering and separating to obtain Fe2O3Mainly filter material and pure rare earth sulfate leaching liquid. The pH value of the obtained rare earth sulfate leaching solution is measured to be 5.5, and the concentration of iron ions is measured to be 0.025 g/L. The total content of the rare earth oxide precipitated in the rare earth sulfate leaching solution is measured by an oxalic acid gravimetric method, and the total recovery rate of the rare earth is 95.6 percent according to the ratio of the total content of the rare earth oxide in the initially added neodymium iron boron oxide material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (8)
1. A method for selectively sulfating and recovering rare earth in neodymium iron boron waste is characterized by comprising the following steps:
s1, preprocessing neodymium iron boron waste materials: crushing, grinding and oxidizing and roasting the unoxidized neodymium iron boron waste or partially oxidized neodymium iron boron waste, and completely oxidizing elements in the neodymium iron boron waste into corresponding high-valence oxides;
s2, sulfating the fully oxidized neodymium iron boron material, converting the rare earth elements in the neodymium iron boron waste material into corresponding rare earth sulfate, wherein the iron element is still Fe2O3The other elements are mainly in an oxide state, and a small part of the elements are in a sulfate state;
and S3, putting the sulfated and roasted material into water, filtering and washing to obtain the pure rare earth sulfate leaching solution.
2. The method for selectively sulfating and recovering the neodymium iron boron waste material according to claim 1, wherein the rare earth in the neodymium iron boron waste material is mainly Nd after being oxidized and roasted2O3And NdFeO3Two structural types of phase forms exist.
3. The method for selectively sulfating and recycling the ndfeb waste according to claim 1, wherein the fully oxidized ndfeb material is further finely ground to a particle size of 3-100 μm before the sulfation treatment.
4. The method for selectively sulfating recycled NdFeB wastes according to claim 1, wherein the sulfation treatment in S2 comprises the steps of: uniformly mixing the finely ground neodymium iron boron oxide material and a solid sulfation reactant, briquetting, and then selectively roasting, or directly placing the finely ground neodymium iron boron oxide material in a gas sulfation reactant for selective sulfation roasting.
5. The method for selectively sulfating and recovering the neodymium iron boron waste material according to claim 4, wherein the solid sulfation reactant is anhydrous ferric sulfate or ferric sulfate with crystal water; the gas sulfation reactant is waste gas SO generated by oxidizing roasting and/or sulfating roasting of sulfide ore3-SO2-O2And (4) mixing the gases.
6. The method for selectively sulfating and recovering neodymium iron boron waste material according to claim 4, wherein the solid sulfation reactant is added in an amount that RE in the neodymium iron boron oxidized material is added2O31.0-3.0 times of theoretical amount when the sulfate is completely sulfated; the RE2O3Comprising a single RE2O3And NdFeO3RE in (1)2O3。
7. The method for selectively sulfatizing recycled neodymium iron boron waste material according to claim 4, characterized in that the conditions of the selective roasting or selective sulfatizing roasting are as follows: roasting at 600-750 ℃ for 0.5-3 h.
8. The method for selectively sulfating recycled neodymium iron boron waste material according to claim 1, wherein in the S3: adding the material after sulfating roasting treatment into deionized water at 25-50 ℃, stirring for 1-3 hours, filtering, and washing to obtain pure rare earth sulfate leaching solution and Fe2O3The main filtrate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114075626A (en) * | 2020-08-20 | 2022-02-22 | 厦门稀土材料研究所 | Method for recovering rare earth metals in rare earth permanent magnet waste through hydrothermal method solution extraction integration |
| CN115305347A (en) * | 2022-08-27 | 2022-11-08 | 苏州金之翼新材料科技有限公司 | Method for preparing zinc ferrite from neodymium iron boron waste |
| CN115386722A (en) * | 2022-08-30 | 2022-11-25 | 苏州金之翼新材料科技有限公司 | Method for separating rare earth and iron from pyrite roasting neodymium iron boron waste |
| CN116377521A (en) * | 2022-12-30 | 2023-07-04 | 中国科学院江西稀土研究院 | Method for recycling mixed rare earth from NdFeB waste |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719674A (en) * | 2012-07-13 | 2012-10-10 | 赣县金鹰稀土实业有限公司 | Method for extracting rare earth from oxidized neodymium iron boron waste |
| CN103146925A (en) * | 2013-03-25 | 2013-06-12 | 安徽天泽矿业科技发展有限公司 | Method of recycling rear earth from neodymium iron boron waste |
| US20160068929A1 (en) * | 2014-09-08 | 2016-03-10 | Patrick R. Taylor | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING |
| KR101662445B1 (en) * | 2015-05-07 | 2016-10-04 | 주식회사 에이.엠.씨 | The selective leaching method of only the rare earth elements in the NdFeB magnet scrap |
| CN108103318A (en) * | 2017-12-24 | 2018-06-01 | 江西理工大学 | A kind of method of Selectively leaching neodymium iron boron greasy filth middle rare earth |
| KR101935826B1 (en) * | 2017-09-28 | 2019-01-07 | 한국지질자원연구원 | Method for the separation of Nd and Dy by use of REE-sulfate double salt precipitation |
| CN109666801A (en) * | 2019-03-07 | 2019-04-23 | 中稀天马新材料科技股份有限公司 | A kind of method of recovering rare earth element in high silicon low content neodymium iron boron waste material |
-
2020
- 2020-02-18 CN CN202010100059.3A patent/CN111187927A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719674A (en) * | 2012-07-13 | 2012-10-10 | 赣县金鹰稀土实业有限公司 | Method for extracting rare earth from oxidized neodymium iron boron waste |
| CN103146925A (en) * | 2013-03-25 | 2013-06-12 | 安徽天泽矿业科技发展有限公司 | Method of recycling rear earth from neodymium iron boron waste |
| US20160068929A1 (en) * | 2014-09-08 | 2016-03-10 | Patrick R. Taylor | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING |
| KR101662445B1 (en) * | 2015-05-07 | 2016-10-04 | 주식회사 에이.엠.씨 | The selective leaching method of only the rare earth elements in the NdFeB magnet scrap |
| KR101935826B1 (en) * | 2017-09-28 | 2019-01-07 | 한국지질자원연구원 | Method for the separation of Nd and Dy by use of REE-sulfate double salt precipitation |
| CN108103318A (en) * | 2017-12-24 | 2018-06-01 | 江西理工大学 | A kind of method of Selectively leaching neodymium iron boron greasy filth middle rare earth |
| CN109666801A (en) * | 2019-03-07 | 2019-04-23 | 中稀天马新材料科技股份有限公司 | A kind of method of recovering rare earth element in high silicon low content neodymium iron boron waste material |
Non-Patent Citations (1)
| Title |
|---|
| 汪金良: "基于硫酸减量化从钕铁硼废料中选择性转型分离稀土", 《过程工程学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075626A (en) * | 2020-08-20 | 2022-02-22 | 厦门稀土材料研究所 | Method for recovering rare earth metals in rare earth permanent magnet waste through hydrothermal method solution extraction integration |
| CN114075626B (en) * | 2020-08-20 | 2024-01-02 | 厦门稀土材料研究所 | Method for integrally recovering rare earth metals in rare earth permanent magnet waste by utilizing hydrothermal method |
| CN115305347A (en) * | 2022-08-27 | 2022-11-08 | 苏州金之翼新材料科技有限公司 | Method for preparing zinc ferrite from neodymium iron boron waste |
| CN115386722A (en) * | 2022-08-30 | 2022-11-25 | 苏州金之翼新材料科技有限公司 | Method for separating rare earth and iron from pyrite roasting neodymium iron boron waste |
| CN116377521A (en) * | 2022-12-30 | 2023-07-04 | 中国科学院江西稀土研究院 | Method for recycling mixed rare earth from NdFeB waste |
| CN116377521B (en) * | 2022-12-30 | 2024-04-16 | 中国科学院江西稀土研究院 | Method for recycling mixed rare earth from NdFeB waste |
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